CN107445825A - A kind of method that molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate - Google Patents
A kind of method that molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate Download PDFInfo
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Abstract
A kind of method that molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate, it is related to a kind of method for preparing industrial chemicals, using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, used catalyst is the different topology structure molecular sieve that doped metallic elements are modified, in system with the presence of suitable quantity of water under the premise of, a step high conversion, the synthesizing methyl glycolate of high selectivity（MG）.Two kinds of product ethanol acid methyl esters（MG）, methoxy menthyl acetate（MMAc）Boiling point difference is larger, is separated product subsequently through simple distillation can.The one-step synthesis methyl glycollate and by-product methoxy menthyl acetate method opened up, in 130 DEG C of reaction temperature, reaction pressure 6.0MPa, under the h of reaction time 6 reaction condition, the 5%Ni/Y prepared using equi-volume impregnating is used as catalyst, DMM conversion ratios are up to 89.59%, MG selectivity reachable 80.40%, and catalyst stabilization uses 2000 h non-inactivations.
Description
Technical field
The present invention relates to a kind of method for preparing industrial chemicals, and glycolic is prepared more particularly to a kind of molecular sieve catalyst
The method of methyl esters and by-product methoxy menthyl acetate.
Background technology
Methyl glycollate（HOCH2COOCH3）, english abbreviation MG is a kind of liquid that is colourless, having euosmia, fusing point 74
DEG C, 150 DEG C of boiling point, density 1.168g/cm3, water is dissolved in, and alcohol and ether can be dissolved in any proportion.Methyl glycollate have α-
H, hydroxyl and ester functional groups, therefore it has the chemical property of alcohol and ester concurrently, and oxonation, hydrolysis, ammonification can occur
Reaction, oxidation reaction etc..Methyl glycollate is the fine solvent of many celluloses, resin and rubber in itself, is soluble in nitro fibre
Tie up element, cellulose acetate, polyvinyl acetate etc..Methyl glycollate is also the important intermediate of organic synthesis and pharmaceutical synthesis,
For example, different tricuspid ester alkali with active anticancer and the like can be synthesized as intermediate using methyl glycollate.Glycolic first
Ester is also the raw material for synthesizing some anti-carrier additives for improving lubricating oil crushing resistance and wearability.
Many important downstream product can be synthesized by raw material of methyl glycollate.For example, methyl glycollate is anti-through carbonylation
Should synthesize malonic acid monomethyl ester, during 70 DEG C of malonic acid monomethyl ester on acid cation exchange resin reaction generation malonic acid dimethyl
Ester；Methyl glycollate synthesizes DL- glycine through aminating reaction；Methyl glycollate obtains large chemical products second two by hydrogenation
Alcohol；Methyl glycollate hydrolyzes to obtain glycolic, and glycolic is mainly used as the cleaning agent of boiler, tellite, while ethanol
Sour polycondensation can generate polyglycolic acid, and polyglycolic acid is a kind of biodegradable material, and the absorbable medical material of human body；Second
The oxidative dehydrogenation of alkyd methyl esters generates glyoxalic acid methylester, and the latter's hydrolysis can obtain glyoxalic acid.Ethylene glycol, dimethyl malenate, sweet ammonia
Acid, glycolic and glyoxalic acid are all current domestic and international chemical products in short supply or more in short supply.
Consulting literatures understand that methyl glycollate mainly has following several synthetic methods：
（One）With glyoxal and methanol one-step synthesis methyl glycollate
HCOCOH+CH3OH → HOCH2COOCH3+H2O...................................(1)
Mitsui East Asia KCC is using glyoxal or its acetal and methanol as raw material, with Al (NO3)3·9H2O
For catalyst, 160 DEG C of reaction temperature, react and methyl glycollate is obtained after 0.5 h, glyoxal conversion ratio is up to 98%, glycolic first
The selectivity of ester is 97%.But raw material glyoxal is poisonous, there are strong impulse effect, and the % of in the market 40 to skin and mucous membrane
The price of glyoxal is at 8000 yuan/ton or so, therefore the method is unfavorable for large-scale industrial production.
（Two）Dimethoxym ethane and formic acid method
Texaco Oil E.L. Yeakey et al. use CH3OCH2OCH3(dimethoxym ethane) and HCOOH are raw material, are being had
In the presence of machine peroxide, and alkyl glycolate ester is prepared under non-acidic conditions, but the shortcomings that the method be reaction
Product is difficult to separate.
（Three）Coupling method
The method uses methyl formate and metaformaldehyde（Or paraformaldehyde is）For raw material, using acidic catalyst synthesizing of glycolate first
Ester.
HCOOCH3+HCHO→ HOCH2COOCH3...................................(2)
J.S. Lee et al. uses the concentrated sulfuric acid or organic sulfonic acid as catalyst, there is methyl glycollate in reaction product, glycolic and
Methyl formate, the problem of product is difficult to separation be present.Kunming University of Science and Technology's Li Zhi cutting edges of a knife or a sword et al. use peroxophosphoric acid as catalyst, ethanol
The yield of sour methyl esters is 59.06 %, but the perishable reactor of strong acid and brings liquid waste processing problem.Mitsubishi chemical company adopts
It is raw material with methyl formate and formaldehyde Huo trioxanes, even phosphomolybdic acid, montmorillonite or cationic ion-exchange resin etc. are catalyst, reaction
Product has methoxy menthyl acetate, methoxyacetic acid, methyl glycollate, oxalic acid methyl ether etc., though the method solves etching problem,
Need higher reaction pressure.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences is urged using carbonyl copper (I) or silver-colored (the I)-sulfuric acid of carbonyl
Agent system, the yield of methyl glycollate is 36.20%.
（Four）Chloroactic acid method
ClCH2COOH+NaOH → HOCH2COOH +NaCl............................(3)
2HOCH2COOH → 2HOCH2COOCH3.....................................(4)
The method is to mix monoxone with sodium hydroxide solution, heating water bath, is evaporated under reduced pressure.Sodium chloride is filtered out, is added in oil bath
Heat obtains paste liquid, adds methanol and the concentrated sulfuric acid afterwards, flow back to obtain methyl glycollate.The shortcomings that method is that monoxone preparation is tired
Difficulty, and monoxone is serious to equipment corrosion.
（Five）Formaldehyde and hydrogen cyanide addition process
HCHO + HCN → HOCH2CN → HOCH2COOH → HOCH2COOCH3..........(5)
The method is that with hydrogen cyanide addition reaction occurs for formaldehyde under sulfuric acid catalysis, obtains hydroxyacetonitrile, then hydrolyzes, is esterified and can obtain
To the methyl glycollate that gross production rate is 80 %.
（Six）Hydrogenation of Dimethyl Oxalate reducing process
(COOCH3) 2 + H2→ HOCH2COOCH3+CH3OH....................................(6)
Italy uses H4Ru(CO)8(PBu3)2Ru(CO)2、(CH3COO)2(PBu3)2、[ ( Ph3P) ( Ph2P) RuH2]2K2
For catalyst, under the conditions of 180 DEG C of reaction temperature, the 2MPa of Hydrogen Vapor Pressure 13., methyl glycollate yield is up to 100 %, but the method
Using organic precious metal as catalyst, preparation technology is complicated, expensive and be difficult to reclaim；Japan uses carried copper and silver
Catalyst, dimethyl oxalate conversion ratio are 90. 2 %, and methyl glycollate yield is 68 %.
（Seven）Formaldehyde carbonylation -ester is combined to method
HCHO+CO+H2O → HOCH2COOH........................................(7)
HOCH2COOH +CH3OH → HOCH2COOCH3....................................(8)
Soumay Sano H et al. exist formalin and CO under the catalyst action such as the concentrated sulfuric acid or boron trifluoride
Generation glycolic is first condensed under 70.9MPa and hot conditions, glycolic and methanol esterification are then generated into methyl glycollate, the method
Used catalyst has severe corrosive and reaction pressure is very high, therefore is unfavorable for large-scale industrial production.Japan
Industrial Co., Ltd of Mitsubishi Chemical and German Hirst company are respectively adopted heteropoly molybdic acid, miscellaneous more wolframic acids and highly acidic cation and handed over
It is catalyst to change resin etc., and oxonation pressure can be down to 5.9 MPa, and methyl glycollate selectively also greatly improves, but the method
It is serious to equipment corrosion using strongly acidic catalyst, and be reaction under high pressure, it is higher to equipment requirement.A.T.Bell et al. is used
Methyl formate replaces gaseous CO to carry out carbonylation with formaldehyde, but is ratedeterming step because methyl formate decomposes release CO,
Influence catalytic perfomance.
As fully visible, synthetic route to be all present long for the synthetic method of methyl glycollate at present, and feed stock conversion is low or production
The problems such as product are selectively low, and building-up process pollutes environment.
The content of the invention
It is an object of the invention to provide a kind of molecular sieve catalyst to prepare methyl glycollate and by-product methoxyacetic acid first
The method of ester, the present invention is using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, to open up one
The method of synthesizing methyl glycolate and by-product methoxy menthyl acetate new way.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method that molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate, methods described is with dimethoxym ethane
For solvent, trimerization, four poly- or sources that paraformaldehyde is as formaldehyde, using metal-modified different topology structure molecular sieve as work
Property component, in system with the presence of suitable quantity of water under the premise of, a step high conversion, the synthesizing methyl glycolate of high selectivity（MG）；
The mol ratio of raw material DMM and aldehyde radical is 0.1:1-5:1, CO reaction pressure 0.1-20MPa, 50-250 DEG C of reaction temperature, catalyst
Dosage is the 0.1-3wt % of material quality, and reactive mode is two kinds of still reaction and continuous fixed bed reaction or continuous；Including following mistake
Journey：
Aldehyde radical, trimerization in dimethoxym ethane, four poly- or sources that paraformaldehyde is as aldehyde radical, dimethoxym ethane are used as solvent and first simultaneously
Epoxide provides presoma, largely dissolves trimerization, four poly- or paraformaldehydes, under water and catalyst existence condition, trimerization, four gather
Or paraformaldehyde separates out formaldehyde in dimethoxym ethane middle reaches and participates in reaction；Under the premise of water and a large amount of dimethoxym ethanes are present, dimethoxym ethane can
Reacted with water, generate DMM2, and methanol is slowly released, such as equation（1）It is shown；
2CH3OCH2OCH3 + H2O →CH3OCH2OCH2OCH3(DMM2)+ 2CH3OH............(1)
The methanol slowly released, esterification, such as reaction equation occurs under a large amount of glycolic existence conditions（2）, generation
MG and H2O：
HOCH2COOH +CH3OH → HOCH2COOCH3 +H2O...............................(2)
The reaction can consume glycolic and methanol simultaneously；With reaction（2）Carry out, glycolic and methanol are constantly consumed, meeting
Formaldehyde oxonation and methanol release reaction is promoted to be carried out to positive reaction；Reaction（2）The water of generation equally promotees as reactant
Enter reaction equation（1,3）Carried out to positive direction；
HCHO+CO+H2O → HOCH2COOH.........................................(3)
The reaction system can be carried out under low water conditions, and the effect of water participates in reaction and given birth to again as product similar to catalyst
Into；This method avoid the first step in two-step method must have a large amount of water to participate in reacting as reactant, and the presence of water can be notable
Reduce the carbonylation efficiency of acid catalyst；
Oxonation generation methoxy menthyl acetate can also occur for solvent DMM itself（MMAc）, such as equation（4）It is shown；MMAc
Itself it is a kind of medicine intermediate of high added value, and MMAc dissolubilities are splendid, not only can be with dissolved organic matter, but also can
To be dissolved each other with water arbitrary proportion, it can promote again during the course of the reaction and dissolve formaldehyde, while largely can dissolve in gas phase
CO, make catalyst surface in liquid phase have an opportunity to contact more CO, be obviously improved CO and aldehyde radical ratio in liquid phase, promote oxonation
Progress；
CH3OCH3OCH3+CO → CH3OCH2COOCH3(MMAc)............................(4)。
The method that a kind of described molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate, it is described to urge
Agent is included by metal-modified Hydrogen MCM-22 molecular sieves, Hydrogen ZSM-35 molecular sieve, Hydrogen ZSM-5 molecular sieve, Hydrogen
One or more in modenite, Hydrogen Y molecular sieve, Hydrogen Beta molecular sieves.
The method that a kind of described molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate, it is described not
Structure type with species topological structure catalyst includes at least one of MWW, FER, MFI, Y, FAU, BEA；Different topology
The atomic ratio of silicon and aluminium is Si/Al=3 ~ 100 in the molecular sieve catalyst of structure.
A kind of described molecular sieve catalyst prepares the method for methyl glycollate and by-product methoxy menthyl acetate, the gold
Belong to modified molecular screen to prepare through infusion process, ion-exchange or in-situ synthesis.
A kind of described molecular sieve catalyst prepares the method for methyl glycollate and by-product methoxy menthyl acetate, the gold
Category atom is located in framework of molecular sieve or in molecular sieve pore passage.
A kind of described molecular sieve catalyst prepares the method for methyl glycollate and by-product methoxy menthyl acetate, the gold
Belong to for the one or more in copper, silver, iron, cobalt, nickel and gallium.
A kind of described molecular sieve catalyst prepares the method for methyl glycollate and by-product methoxy menthyl acetate, the gold
It is 0.005 ~ 5%wt% to belong to weight/mass percentage composition of the atom in molecular sieve.
A kind of described molecular sieve catalyst prepares the method for methyl glycollate and by-product methoxy menthyl acetate, the gold
The modified one or more using in the chlorate of metal, nitrate, acetate, oxalates of category, preferably nitrate or acetate.
The method that a kind of described molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate, it is described to urge
Contain the binding agent being made up of any one or a few in aluminum oxide, silica, titanium oxide or magnesia in agent；It is described viscous
Knot agent accounts for 0 ~ 70wt% of total catalyst weight.
Advantages of the present invention is with effect：
The method that the present invention opens a brand-new methyl glycollate and by-product methoxy menthyl acetate, and using homemade
The reaction of metal-modified catalyst, it is advantageous that reaction system can be carried out under low water conditions, water participates in reaction and again
Generated as product, avoiding the first step in two-step method there must be a large amount of water to participate in reacting as reactant, simultaneous reactions process
The methoxy menthyl acetate of middle generation is a kind of medicine intermediate of high added value in itself, can largely dissolve the CO in gas phase,
Make catalyst surface in liquid phase have an opportunity to contact more CO, be obviously improved CO and aldehyde radical ratio in liquid phase, promote oxonation
Carry out.Methyl glycollate（MG）, methoxy menthyl acetate（MMAc）The two boiling point difference is larger, subsequently through simple distillation just
Product can be separated.
Brief description of the drawings
Differential responses temperature turns to methyl glycollate when Fig. 1 is using 5% Ni/Y of equi-volume impregnating preparation as catalyst
The influence figure of rate.
Embodiment
With reference to embodiment, the present invention is described in detail.
The present invention is using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, with metal-modified
Different topology structure molecular sieve is active component, in system with the presence of suitable quantity of water under the premise of, a step high conversion, high selectivity
Synthesizing methyl glycolate（MG）.The methyl glycollate of document and patent report synthesis before has to pass through two steps：It is first first
Aldehyde carbonyl groups turn to glycolic, and it is methyl glycollate then to add a large amount of methanol esterifications.In the brand-new one-step synthesis method route, first contracting
Aldehyde radical, trimerization in aldehyde, four poly- or sources that paraformaldehyde is as aldehyde radical, dimethoxym ethane is simultaneously as solvent and methoxyl group offer
Presoma effectively can largely dissolve trimerization, four poly- or paraformaldehydes（Because dimethoxym ethane has aldehyde radical in itself, to the molten of aldehyde radical
Solution and the free effect of promotion are very good）, it is trimerization, four poly- or paraformaldehyde can be in first under water and catalyst existence condition
More exist in acetal in the form of free formaldehyde.As aldehyde radical ratio and reaction temperature gradually rise in system, free first
With water and CO carbonylation occurs for aldehyde first, generates glycolic, such as equation（7）It is shown.
HCHO+CO+H2O→ HOCH2COOH.......................................(7)
Meanwhile under the premise of water and a large amount of dimethoxym ethanes are present, dimethoxym ethane can react with water, generate DMM2, and slowly release
Methanol, such as equation（8）It is shown.
2CH3OCH2OCH3+H2O→CH3OCH2OCH2OCH3(DMM2)+ 2CH3OH......(8)
The methanol slowly released, it is more prone to that esterification, rather than itself dehydration occurs under a large amount of glycolic existence conditions
Reaction, because relative to methanol, there is a large amount of glycolics in system.Therefore, a large amount of glycolics of generation are easily with discharging
Esterification, such as reaction equation occur for methanol（9）, generate MG and H2O, the reaction can consume glycolic and methanol simultaneously.
With reaction（9）Carry out, glycolic and methanol are constantly consumed, and can promote formaldehyde oxonation and methanol release reaction to just
Reaction is carried out.Reaction（9）The water of generation equally promotes reaction equation as reactant（7,8）Carried out to positive direction.The reaction
System can be carried out under low water conditions, and the effect of water participates in reaction and generated again as product similar to catalyst.Thus keep away
Having exempted from the first step in two-step method must have a large amount of water to participate in reacting as reactant, and the presence of water can significantly reduce acid catalyst
Carbonylation efficiency.
HOCH2COOH+CH3OH→ HOCH2COOCH3 +H2O.........................(9)
Oxonation generation methoxy menthyl acetate can also occur for solvent DMM itself（MMAc）, such as equation（10）It is shown.MMAc
Itself it is a kind of medicine intermediate of high added value, and MMAc dissolubilities are splendid, not only can be with dissolved organic matter, but also can
To be dissolved each other with water arbitrary proportion, it can promote again during the course of the reaction and dissolve formaldehyde, while largely can dissolve in gas phase
CO, make catalyst surface in liquid phase have an opportunity to contact more CO, be obviously improved CO and aldehyde radical ratio in liquid phase, promote oxonation
Progress.
CH3OCH3OCH3+CO → CH3OCH2COOCH3(MMAc).......................(10)
The catalyst is included by metal-modified Hydrogen MCM-22 molecular sieves, Hydrogen ZSM-35 molecular sieve, ZSM-5 points of Hydrogen
One or more in sub- sieve, h-mordenite, Hydrogen Y molecular sieve, Hydrogen Beta molecular sieves.
The structure type of the variety classes topological structure catalyst is included in MWW, FER, MFI, Y, FAU, BEA at least
It is a kind of.The atomic ratio of silicon and aluminium is Si/Al=3 ~ 100 in the molecular sieve catalyst of different topology structure.
The metal-modified different topology structure molecular sieve can be prepared through infusion process, ion-exchange, in-situ synthesis.
The metallic atom is located in framework of molecular sieve or in molecular sieve pore passage.
The metal is the one or more in copper, silver, iron, cobalt, nickel and gallium.
Weight/mass percentage composition of the metallic atom in molecular sieve is 0.005 ~ 5%wt%.
The metal-modified one or more using in the chlorate of metal, nitrate, acetate, oxalates.It is preferred that
Ground, the metal salt are selected from nitrate or acetate.
Contain the binding agent being made up of any one or a few in aluminum oxide, silica or magnesia in the catalyst；
The binding agent accounts for 5 ~ 50wt% of total catalyst weight.
Embodiment 1：Catalyst preparation example
H-Y catalyst
By 100 grams of roasting Na-Y（Si/Al=6.5）Molecular sieve is exchanged three times with 0.5mol/L ammonium nitrate, 2 hours every time, is used
Deionized water is washed, and is dried, and is calcined 4 hours at 550 DEG C, and the 1# catalyst of 20-40 mesh is prepared respectively through extruding.
Support type M/Y catalyst
The M/Y catalyst of support type 5% is prepared using equi-volume impregnating.Respectively by 4.32 g Cu (NO3)2·3H2O、3.04 g
AgNO3·3H2O、4.32gFe(NO3)3、5.21g Co(NO3)2·6H2O 、5.21 g Ni(NO3)2·6H2O and 4.58 g Ga
(NO3)3It is dissolved in 18 mL deionized waters and is made into corresponding nitrate aqueous solution.20g 1# H-Y molecular sieve catalysts are added respectively
Enter in above-mentioned nitrate aqueous solution, stand 24 hours, then through separation, deionized water washing, gained sample is in 120 DEG C of baking ovens
To dry 12 hours, dried sample is placed in Muffle furnace, is warming up to 550 DEG C with 2 DEG C/min heating rate, is calcined 4h, point
2#, 3#, 4#, 5#, 6#, 7# catalyst are not prepared.
Respectively with Cu (NO3)2·3H2O、AgNO3·3H2O、Fe(NO3)3And Ga (NO3)3For raw material, according to metallic atom
Content is 0.05%, method with it is above-mentioned it is consistent under conditions of 8#, 9#, 10#, 11# catalyst is prepared.
Respectively with Co (NO3)2·6H2O、Ni(NO3)2·6H2O and Ga (NO3)3For raw material, it is according to metal atom content
2%, method with it is above-mentioned it is consistent under conditions of 12#, 13#, 14# catalyst is prepared.
It is 1% according to metal atom content respectively using copper acetate, nickel acetate as raw material, is configured to ethanol solution, dipping system
Into 15#, 16# catalyst.
Ion-exchange type M-Y catalyst
Respectively by 300mL0.15mol Cu (NO3)2·3H2O、AgNO3·3H2O、Fe(NO3)3、Co(NO3)2·6H2O、Ni
(NO3)2·6H2O and Ga (NO3)3The aqueous solution and 20g 1#H-Y molecular sieves insert flask, at 80 DEG C, under conditions of cooling for reflux under
Stir process 2 hours, solid-to-liquid ratio 1:15.It is separated by filtration, deionized water washing, repeats the above steps 2 times, 120 DEG C of dryings 12 are small
When, sample is placed in Muffle furnace after drying, and is warming up to 550 DEG C with 2 DEG C/min heating rate, is calcined 4h, obtain 17#, 18#,
19#, 20#, 21#, 22# catalyst.
Fabricated in situ molecular screen containing heteroatom
Directly add Cu (NO respectively in building-up process3)2·3H2O、AgNO3·3H2O、Fe(NO3)3、Co(NO3)2·6H2O、
Ni(NO3)2·6H2O and Ga (NO3)3, metal atom content design flow is 1.5%, after the sample for synthesizing to obtain is calcined, is used
0.5mol/L ammonium nitrate exchanges three times, 2 hours every time, is washed with deionized, and dries, and is calcined 4 hours at 550 DEG C, through extruding
23#, 24#, 25#, 26#, 27#, 28# catalyst of 20-40 mesh is prepared.
Preformed catalyst
Respectively using aluminum oxide, silica and magnesia as binding agent, binder content 20%, 25# samples are molecular screen primary powder,
Extruded moulding after molecular sieve, binding agent and 10% dust technology are well mixed, be prepared 29 through processing, 30,31# catalyst.
Aluminum oxide is binding agent respectively, and content is respectively that 10%, 50%, 25# samples are molecular screen primary powder, molecular sieve, bonding
Extruded moulding after agent and 10% dust technology are well mixed, 32#, 33# catalyst is prepared through processing.
Embodiment 2：The reactivity worth of catalyst
By the gained catalyst fines of embodiment 1 through tabletting, pulverize, sieve 40 ~ 60 obtained mesh samples and be used for synthesizing of glycolate first
Ester and by-product methoxy menthyl acetate reactivity worth measure.20 kg dimethoxym ethanes are weighed respectively（DMM）, 3.9 kg metaformaldehydes, 4
Kg water, the various g of catalyst 300 made from embodiment 1 are fitted into reactor, then pass to 1.0 MPa CO gas, if
After not omitting sky gas reactor in printing, aforesaid operations are repeated 2 times（Air in replacement reaction kettle）.It is passed through again a certain amount of（6.0 MPa）
Gas leaked hunting, and stand 15 min, pressure gauge registration do not decline, and represents that device does not have gas leakage, then empties in kettle
Gas, is filled with 6.0 MPa CO gases into kettle again, heat temperature raising, 500 revs/min of reactor mixing speed, and reaction pressure is
6.0MPa, 130 DEG C of reaction temperature, reaction time are 6 h, and reaction result is as shown in table 1.
Influence of the different catalysts of table 1 to feed stock conversion and selectivity of product
Reaction condition：20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g catalyst, 130 DEG C of reaction temperature, reaction
Pressure 6.0MPa, the h of reaction time 6.
As can be seen from Table 1, it is significantly improved by metal-modified rear catalyst reactivity, at different method of modifying
The catalyst of reason is different to reaction impact effect.In 130 DEG C of reaction temperature, reaction pressure 6.0 MPa, 6 h of reaction time, with
5% Ni/Y catalyst prepared by equi-volume impregnating has optimum response active, and DMM conversion ratios are selective up to 89.59%, MG
Up to 80.40%.
Embodiment 3
Respectively with Hydrogen Y molecular sieve, Hydrogen MCM-22 molecular sieves, Hydrogen ZSM-35 molecular sieve, Hydrogen ZSM-5 molecular sieve, Hydrogen
Modenite, Hydrogen Beta molecular sieves are as metal-modified catalyst carrier, with the preparation method system of 6# catalyst in embodiment 1
Standby metal-modified catalyst, is respectively labeled as 6#, 6# MCM-22,6# ZSM-35,6# ZSM-5,6 # MOR, 6# beta catalysts,
Gained catalyst fines through tabletting, pulverize, sieve obtained 40 ~ 60 mesh samples and be used for synthesizing methyl glycolate and by-product methoxyl group
Methyl acetate reactivity worth determines.20 kg dimethoxym ethanes are weighed respectively（DMM）, 3.9 kg metaformaldehydes, 4 kg water are above-mentioned various
The g of catalyst 300 is fitted into reactor, then passes to 1.0 MPa CO gas, if after not omitting sky gas reactor in printing, repeating
Aforesaid operations 2 times（Air in replacement reaction kettle）.It is passed through again a certain amount of（6.0 MPa）Gas leaked hunting, and stand 15
Min, pressure gauge registration do not decline, and represent that device does not have gas leakage, then empty gas reactor, be filled with 6.0 into kettle again
MPa CO gases, heat temperature raising, 500 revs/min, reaction pressure 6.0MPa of reactor mixing speed, 130 DEG C of reaction temperature, instead
It is 6 h between seasonable, reaction result is as shown in table 2.
Influence of the catalyst different topology structure carrier of table 2 to feed stock conversion and selectivity of product
Reaction condition：20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g catalyst, 130 DEG C of reaction temperature, reaction
Pressure 6.0MPa, the h of reaction time 6.
As can be seen from Table 2, the metal-modified catalyst using different topology structure molecular sieve as carrier influences on reaction
Effect is different.In 130 DEG C of reaction temperature, reaction pressure 6.0 MPa, 6 h of reaction time, the 5% of carrier is used as using Y molecular sieve
Ni/Y catalyst has optimum response activity, and DMM conversion ratios are that 89.59%, MG selectivity is 80.40%.
Embodiment 4
20 kg dimethoxym ethanes are weighed respectively（DMM）, 3.9 kg metaformaldehydes, 4 kg water, 300 g 6# catalyst loading reactor
In, 1.0 MPa CO gas are then passed to, if after not omitting sky gas reactor in printing, repeating aforesaid operations 2 times（Displacement reaction
Air in kettle）.It is passed through again a certain amount of（6.0 MPa）Gas leaked hunting, and stand 15 min, pressure gauge registration without under
Drop, represent that device does not have gas leakage, then empty gas reactor, be filled with 6.0 MPa CO gases into kettle again, heat temperature raising, instead
Answer 500 revs/min of kettle mixing speed, the MPa of reaction pressure 6.0, reaction temperature is respectively 90 DEG C, 100 DEG C, 110 DEG C, 130 DEG C, 150
DEG C, the h of reaction time 6, reaction result is as shown in table 3.
Influence of the differential responses temperature of table 3 to feed stock conversion and selectivity of product
Reaction condition：20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g 6# catalyst, reaction pressure 6.0MPa,
The h of reaction time 6.
As can be seen from Table 3, as the rise of reaction temperature, DMM conversion ratios gradually increase, when reaction temperature is 130 DEG C
When, DMM conversion ratios are 89.59%, and when reaction temperature is 150 DEG C, DMM conversion ratios are 93.12%.With the liter of reaction temperature
Height, MMAc Mass Selectives first increase to be reduced afterwards, and in 110 DEG C of reaction temperature, MMAc Mass Selectives are up to 15.41%；
The variation tendency of MG Mass Selectives is identical with MMAc, and in 130 DEG C of reaction temperature, MG Mass Selectives are up to
80.40%。
Embodiment 5
20 kg dimethoxym ethanes are weighed respectively（DMM）, 3.9 kg metaformaldehydes, 4 kg water, 300 g6# catalyst are fitted into reactor,
1.0 MPa CO gas are then passed to, if after not omitting sky gas reactor in printing, repeating aforesaid operations 2 times（In replacement reaction kettle
Air）.It is passed through again a certain amount of（6.0 MPa）Gas leaked hunting, and stand 15 min, pressure gauge registration do not decline,
Represent that device does not have gas leakage, then empty gas reactor, be passed through goal pressure CO gases, heat temperature raising, reactor mixing speed
500 revs/min, reaction pressure is respectively 2.0 MPa, 3.0 MPa, 4.0 MPa, 5.0 MPa, 6.0MPa, 8.0 MPa, and 10.0
MPa, 15.0 MPa, 130 DEG C of reaction temperature, the h of reaction time 6, reaction result are as shown in table 4.
Influence of the differential responses pressure of table 4 to feed stock conversion and selectivity of product
Reaction condition：20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 4 kg water, 300 g 6# catalyst, 130 DEG C of reaction temperature,
The h of reaction time 6.
As can be seen from Table 4, with the rise of reaction pressure, CO concentration gradually increases in liquid phase, in system aldehyde radical total amount
Under conditions of certain, CO and aldehyde radical ratio gradually rise, therefore DMM conversion ratios gradually increase, when reaction pressure is 15.0 MPa
When, DMM tends to convert completely.With the rise of reaction pressure, MMAc Mass Selectives are first raised and reduced afterwards, are in reaction pressure
During 5.0 MPa, MMAc Mass Selectives are up to 24.34%.MG Mass Selective is gradual with the rise of reaction pressure
Rise, because reaction pressure raises, CO and aldehyde radical ratio raise in liquid phase, are more beneficial for the generation of aldehyde radical oxonation,
When reaction pressure is 15.0 MPa, MG Mass Selective is up to 91.79%.
Embodiment 6
20 kg dimethoxym ethanes are weighed respectively（DMM）, 3.9 kg metaformaldehydes, 4 kg water, 300 g6# catalyst are fitted into reactor,
1.0 MPa CO gas are then passed to, if after not omitting sky gas reactor in printing, repeating aforesaid operations 2 times（In replacement reaction kettle
Air）.It is passed through again a certain amount of（6.0 MPa）Gas leaked hunting, and stand 15 min, pressure gauge registration do not decline,
Represent that device does not have gas leakage, then empty gas reactor, be passed through 6 MPa CO gases, heat temperature raising, reactor mixing speed 500
Rev/min, the reaction time is respectively 30 min, 1 h, 3 h, 5 h, 6 h, 8 h, 10 h.130 DEG C of reaction temperature, reaction result is such as
Shown in table 5.
As can be seen from Table 5, with the increase in reaction time（0-6 h）, DMM conversion ratios gradually increase, MMAc mass
Gradually increase, MG Mass Selectives similarly increase selectivity.But DMM conversion ratios, MMAc and MG when being more than 6 h between when reacted
Mass Selective is basically unchanged, and reason is the progress with reaction, reaction forward movement, when reacted between when reaching 6 h, reaction
Balance is basically reached, continues to increase the reaction time, each component content no longer changes substantially.
Influence of the differential responses duration of table 5 to feed stock conversion and selectivity of product
Reaction condition：20 kg dimethoxym ethanes, 10 kg paraformaldehydes, 4 kg water, 300 g 6# catalyst, 130 DEG C of reaction temperature, instead
Answer pressure 6.0MPa, the h of air speed 30-1。
Embodiment 7
20 kg dimethoxym ethanes are weighed respectively（DMM）, 3.9 kg metaformaldehydes, 300 g 6# catalyst are fitted into reactor, water plus
Enter amount is respectively dimethoxym ethane quality 3%, 5%, 10%, 20%, 30%, 1.0 MPa CO gas are then passed to, if not omitting in printing
After empty gas reactor, aforesaid operations are repeated 2 times（Air in replacement reaction kettle）.It is passed through again a certain amount of（6.0 MPa）Gas
To be leaked hunting, and stand 15 min, pressure gauge registration does not decline, and represents that device does not have gas leakage, then empties gas reactor, then
It is secondary to be filled with 6.0 MPa CO gases into kettle, heat temperature raising, 500 revs/min of reactor mixing speed, the MPa of reaction pressure 6.0,
130 DEG C of reaction temperature, the h of reaction time 6, reaction result are as shown in table 6.
Influence of the addition of 6 different water of table to feed stock conversion and selectivity of product
Reaction condition：20 kg dimethoxym ethanes, 3.9 kg metaformaldehydes, 300 g 6# catalyst, 130 DEG C of reaction temperature, reaction pressure
6.0MPa, the h of reaction time 6.
As can be seen from Table 6, with the increase of dampening addition, DMM conversion ratios and MMAc Mass Selectives gradually under
Drop, when the addition of water is the 3% of dimethoxym ethane quality, DMM conversion ratios are that 99.98%, MMAc Mass Selectives are 56.87%；When
When the addition of water is the 30% of dimethoxym ethane quality, DMM conversion ratios are that 80.21%, MMAc Mass Selectives are 9.54%.With dampening
The increase of addition, MG Mass Selective first increases to be reduced afterwards, when the addition of water is the 20% of dimethoxym ethane quality, MG's
Mass Selective is up to 84.25%.Because formaldehyde carbonylation needs the water in consumption system, when the addition of water is less
（3%、5%、10%）, in system formaldehyde largely free can not carbonylation generation glycolic, while the addition of water less causes DMM
Discharge that the speed of methanol is slack-off, and these are all unfavorable for MG generation, therefore when the addition of water is less, MG Mass Selectives compared with
It is low.When the addition of water is more（30%）, MG Mass Selectives decline the reason for be that water combines to form with catalyst acid center
H3O+, cause part acid site to be covered with water, catalyst carbonylation activity decrease.It is preferred that the addition of water is dimethoxym ethane quality
20%。
Embodiment 8
In fixed bed reactors, load the g of 6# catalyst 300, material rate is：20 kg dimethoxym ethanes（DMM）, 4 kg water, 3.9
Kg metaformaldehydes, above-mentioned raw materials are pumped into reactor using constant flow pump, air speed is 30 h-1, 130 DEG C of reaction temperature, reaction pressure
Reacted under the MPa of power 6.0, sampling progress chromatography calculating after 200 h, 500 h, 1000h, 2000 h is stablized in reaction respectively, former
Expect that conversion ratio, selectivity of product are as shown in table 7.
The catalyst stability of table 7 is investigated
Reaction condition：20 kg dimethoxym ethanes, 10 kg paraformaldehydes, 4 kg water, 300 g 6# catalyst, 130 DEG C of reaction temperature, instead
Answer pressure 6.0MPa, the h of air speed 30-1。
As can be seen from Table 7,2000 h of reaction experience, feed stock conversion, selectivity of product are basically unchanged, catalyst stabilization
The good, non-inactivation of property.
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (9)
1. a kind of method that molecular sieve catalyst prepares methyl glycollate and by-product methoxy menthyl acetate, it is characterised in that institute
Method is stated using dimethoxym ethane as solvent, the source of trimerization, four poly- or paraformaldehydes as formaldehyde, with metal-modified different topology
Structure molecular screen is active component, in system with the presence of suitable quantity of water under the premise of, a step high conversion, the synthesis second of high selectivity
Alkyd methyl esters（MG）；The mol ratio of raw material DMM and aldehyde radical is 0.1:1-5:1, CO reaction pressure 0.1-20MPa, reaction temperature 50-
250 DEG C, catalyst amount is the 0.1-3wt % of material quality, and reactive mode is two kinds of still reaction and continuous fixed bed reaction or continuous；
Including procedure below：
Aldehyde radical, trimerization in dimethoxym ethane, four poly- or sources that paraformaldehyde is as aldehyde radical, dimethoxym ethane are used as solvent and first simultaneously
Epoxide provides presoma, largely dissolves trimerization, four poly- or paraformaldehydes, under water and catalyst existence condition, trimerization, four gather
Or paraformaldehyde separates out formaldehyde in dimethoxym ethane middle reaches and participates in reaction；Under the premise of water and a large amount of dimethoxym ethanes are present, dimethoxym ethane can
Reacted with water, generate DMM2, and methanol is slowly released, such as equation（1）It is shown；
2CH3OCH2OCH3 + H2O → CH3OCH2OCH2OCH3(DMM2)+ 2CH3OH…………(1)
The methanol slowly released, esterification, such as reaction equation occurs under a large amount of glycolic existence conditions（2）, generation
MG and H2O：
HOCH2COOH +CH3OH → HOCH2COOCH3 +H2O...................................(2)
The reaction can consume glycolic and methanol simultaneously；With reaction（2）Carry out, glycolic and methanol are constantly consumed, meeting
Formaldehyde oxonation and methanol release reaction is promoted to be carried out to positive reaction；Reaction（2）The water of generation equally promotees as reactant
Enter reaction equation（1,3）Carried out to positive direction；
HCHO+CO+H2O → HOCH2COOH…….......................................(3)
The reaction system can be carried out under low water conditions, and the effect of water participates in reaction and given birth to again as product similar to catalyst
Into；This method avoid the first step in two-step method must have a large amount of water to participate in reacting as reactant, and the presence of water can be notable
Reduce the carbonylation efficiency of acid catalyst；
Oxonation generation methoxy menthyl acetate can also occur for solvent DMM itself（MMAc）, such as equation（4）It is shown；MMAc
Itself it is a kind of medicine intermediate of high added value, and MMAc dissolubilities are splendid, not only can be with dissolved organic matter, but also can
To be dissolved each other with water arbitrary proportion, it can promote again during the course of the reaction and dissolve formaldehyde, while largely can dissolve in gas phase
CO, make catalyst surface in liquid phase have an opportunity to contact more CO, be obviously improved CO and aldehyde radical ratio in liquid phase, promote oxonation
Progress；
CH3OCH3OCH3+CO → CH3OCH2COOCH3(MMAc)..........................(4)。
2. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that the catalyst is included by metal-modified Hydrogen MCM-22 molecular sieves, Hydrogen ZSM-35 molecules
One or more in sieve, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y molecular sieve, Hydrogen Beta molecular sieves.
3. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that the structure type of the variety classes topological structure catalyst includes MWW, FER, MFI, Y, FAU, BEA
At least one of；The atomic ratio of silicon and aluminium is Si/Al=3 ~ 100 in the molecular sieve catalyst of different topology structure.
4. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that the metal modified molecular screen is prepared through infusion process, ion-exchange or in-situ synthesis.
5. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that the metallic atom is located in framework of molecular sieve or in molecular sieve pore passage.
6. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that the metal is the one or more in copper, silver, iron, cobalt, nickel and gallium.
7. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that weight/mass percentage composition of the metallic atom in molecular sieve is 0.005 ~ 5%wt%.
8. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that described metal-modified one kind or more using in the chlorate of metal, nitrate, acetate, oxalates
Kind, preferably nitrate or acetate.
9. a kind of molecular sieve catalyst according to claim 1 prepares methyl glycollate and by-product methoxy menthyl acetate
Method, it is characterised in that contain in the catalyst by any one in aluminum oxide, silica, titanium oxide or magnesia or several
The binding agent of kind composition；The binding agent accounts for 0 ~ 70wt% of total catalyst weight.
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